Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
  • C08G2/08—Polymerisation of formaldehyde
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/56—Polyacetals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
  • C08G2/18—Copolymerisation of aldehydes or ketones

Definitions

• This invention relates to the grafting of functional compounds (i.e. compounds with one or two hydroxyl, carboxyl, or amine functional groups) onto a functional polyacetal backbone (i.e., a polymer having recurring --CH 2 O-- units with attached side chain hydroxyl functionality) with diisocyanate coupling agents, and to the resulting graft copolymers thereby obtained.
• a functional polyacetal backbone i.e., a polymer having recurring --CH 2 O-- units with attached side chain hydroxyl functionality
• Oxymethylene polymers represent an important class of engineering resins due to numerous favorable physical properties. For this reason, oxymethylene polymers have a wide range of commercial applications, for example, as parts for automobiles, as plumbing components and a variety of household and personal products.
• oxymethylene polymers are usually blended with a variety of other resins and/or ingredients (e.g., impact modifying agents, flame retardants, light and heat stabilizers, fillers, and the like).
• other resins and/or ingredients e.g., impact modifying agents, flame retardants, light and heat stabilizers, fillers, and the like.
• grafting of functional compounds or polymers onto an functional oxymethylene backbone with diisocyanate coupling agents would present an attractive alternative to blending so as to achieve block copolymers having the desired modified properties and/or to employ such graft copolymers as compatibilizing agents for compositions containing blends of oxymethylene polymer and a polymer with the same backbone as the functional polymer or a polymer which is compatible with the backbone of the functional polymer.
• oxymethylene polymers grafting is usually not possible due to the low level of polyacetal end group functionality --that is, since each oxymethylene molecule carries a maximum of two functional groups, e.g., hydroxyl end groups.
• grafting of functional compounds or polymers onto oxymethylene backbones with diisocyanate coupling agents is accomplished by increasing the reactive sites on the oxymethylene polymers. That is, the oxymethylene polymers employed in the present invention will exhibit increased functionality, in the form of reactive pendant hydroxyl groups. Hence, these oxymethylene polymers with increased hydroxyl functionality may be reacted with suitable functional compounds, diisocyanate coupling agents, and optionally, monofunctional end capping agents so as to obtain the graft copolymers of this invention.
• the preferred oxymethylene polymer backbones onto which the functional compounds are grafted are essentially random copolymers containing oxymethylene units interspersed with higher oxyalkylene units having pendant hydroxyl groups. These pendant functional hydroxyl groups of the higher oxyalkylene units therefore provide reactive sites for the grafting of isocyanate compounds onto the oxymethylene backbone.
• novel graft copolymers of this invention may find usefulness as an engineering resins per se (i.e., as resins in which the functional compounds are chemically bound to the oxymethylene backbone), or as compatibilizing agents so as to compatibilize blends of oxymethylene polymers with other polymers having the same or similar backbones as the backbone of the functional compound or with other polymers that are compatible with the polymer backbone of the functional compound.
• graft copolymers could be used to improve the mechanical and impact properties of blends of oxymethylene polymers with other appropriate polymers through improvement of interfacial adhesion between incompatible polymers.
• novel graft polymers may also find usefulness as modifiers and additives to oxymethylene polymers with improved effectiveness through improved compatibility.
• oxymethylene copolymers having recurring units represented by the following Formulas I, II, and III: ##STR1## where R is a C1-C6 alkyl group, and m and n are integers such that m+n is between 5 and 20,000 and the ratio of units of subscript m to the units of subscript n is between 1:1 and 1000:1; ##STR2## where m, n, and p are integers suoh that m+n+p is between 5 and 20,000 and the ratio of units of subscript m to the units of subscript n+p is between 1:1 and 1000:1; and ##STR3## where q is an integer between 1 and 4, and m and n are integers such that m+n is between 5 and 20,000 and the ratio of units of subscript m to the units of subscript n is between 1:1 and 1000:1.
• oxymethylene copolymers represented by Formulas I-III above may be prepared by the cationic copolymerization of trioxane with cyclic formals having pendant hydroxyl and, particularly, pendant ester functional groups which may subsequently be hydrolyzed to yield a hydroxyl group.
• the pendant ester functional groups in particular, are essentially unreactive (i.e. protected) under polymerization conditions and thus survive the copolymerization process.
• the hydroxyl groups (either present during the copolymerization reaction or ester groups converted to hydroxyl groups during subsequent hydrolysis) will therefore provide reactive sites for grafting of isocyanate compounds according to this invention.
• 07/350,781 (now U.S. Pat. No. 4,975,519) filed even date herewith in the names of Jerry A. Broussard et al and entitled "Novel Polyacetal Terpolymers of Trioxane and ⁇ , ⁇ - and ⁇ , ⁇ -Isomers of Glycerol Formal and Functional Derivatives Thereof"; and U.S. Serial No. 07/350,791 (now U.S. Pat. No.
• Monomers other than trioxane and the cyclic formals or their functionalized derivatives as described in the above-mentioned copending U.S. Applications may also be employed so as to form oxymethylene terpolymers or tetrapolymers--that is, polymers having units in the chain derived from trioxane, cyclic formals or their functionalized derivatives, and the other monomer(s) which may be employed.
• these additional monomers that may be employed are cyclic ethers and cyclic acetals with ethylene oxide, 1,3-dioxolane, 1,3-dioxepane, 1,3-dioxep-5-ene, and 1,3,5-trioxepane being particularly preferred.
• copolymer is intended to encompass any polymer having, as at least part of the polymer chain, structural units derived from trioxane and cyclic formals having pendant hydroxyl or ester functional groups.
• copolymer as used herein and in the accompanying claims to describe the oxymethylene backbones useable in this invention is intended to encompass terpolymers, tetrapolymers, and the like which include structural units in the polymer chain derived from trioxane and cyclic formals or their functionalized derivatives, in addition to other units derived from, e.g., the cyclic ether or cyclic acetal monomers described above, if present during polymerization.
• Any suitable diisocyanate coupling agent may be employed in the practice of the present invention provided that it is capable of reacting with the pendant hydroxyl groups of the oxymethylene backbone and the functional groups (hydroxyl, carboxyl, and amine groups) of the functional compounds to form a graft polymer.
• Suitable diisocyanate coupling agents include 1,4-benzene diisocyanate; 3,3'-dimethyl-4,4'-biphenylenediisocyanate; methylene di(-p-phenylisocyanate); 1,6-hexamethylene diisocyanate; 2,6-toluene diisocyanate; 2,4-toluene diiisocyanate; and mixtures of the same.
• any suitable functional compound may be employed in the practice of the present invention provided that it is capable of reacting with the diisocyanate coupling agents.
• the term "functional compound” is intended to refer to any compound or polymer having one or two functional groups (hydroxyl, carboxyl, or amine groups) per chain, preferably terminal functional groups, which undergo an addition reaction with the diisocyanate coupling agents of the present invention.
• suitable functional compounds may include mono and difunctional polyalkylene oxides, polyesters, polyamides, polyolefins, polydienes, and polysiloxanes.
• suitable functional compounds include the following:
• monofunctional endcapping agents may optionally be used to avoid or minimize crosslinking of the other components used to prepare these polymer grafts.
• Appropriate monofunctional endcapping groups include aliphatic alcohols, aliphatic and aromatic carboxylic acids, and aliphatic and aromatic amines.
• the graft copolymers of the present invention may be prepared by one of three general methods.
• hydroxy functional oxymethylene polymers can be prepared from hydroxy functional oxymethylene polymers, monofunctional compounds, and diisocyanate coupling agents.
• a hydroxy functional oxymethylene polymer POM-OH
• PEG-OH polyethylene glycol monomethyl ether
• toluene diisocyanate O ⁇ C ⁇ N--AR--N ⁇ C ⁇ O
• hydroxy functional oxymethylene polymer difunctional compounds, and diisocyanate coupling agents.
• a hydroxy functional oxymethylene polymer POM--OH
• polyethylene glycol HO--PEG--OH
• toluene diisocyanate O ⁇ C ⁇ N--AR--N ⁇ C ⁇ O
• a hydroxy functional oxymethylene polymer POM--OH
• polyethylene glycol HO--PEG--OH
• toluene diisocyanate O ⁇ C ⁇ N--AR--N ⁇ C ⁇ O
• BuOH n-butanol
• the graft copolymers of the present invention may be prepared in a two stage process in which the functional compounds, diisocyanate coupling agents, and optionally, monofunctional endcapping agents are reacted in an initial step to form isocyanate functional compounds which are reacted with hydroxy functional oxymethylene polymers in a second step. Alternately, they may be prepared in a two stage process in which the hydroxy functional oxymethylene polymers are reacted with a diisocyanate coupling agent to form an isocyanate functional oxymethylene polymer which is reacted with mono- or difunctional compounds in a second step.
• reagents hydroxy functional oxymethylene polymers, diisocyanate coupling agents, mono- and difunctional compounds, and optionally, monofunctional endcapping agents
• Preferred conditions for effecting reaction conditions to graft the functional compounds onto the oxymethylene backbones with diisocyanate coupling agents according to this invention are believed to be well within the skills of those in this art.
• the grafting reaction of functional compounds onto hydroxy functional oxymethylene polymers with diisocyanate coupling agents may be effected in solution in a batch process at elevated temperatures.
• the grafting reaction of functional compounds onto hydroxy functional oxymethylene polymers with diisocyanate coupling agents may also be effected in a polymer melt in a continuous or batch fashion.
• Reaction conditions are chosen to maximize grafting while minimizing degradation of the oxymethylene polymer.
• the preferred solvents and solvent mixtures are those that will dissolve or partially dissolve oxymethylene polymers and the isocyanate functional compounds under mild conditions and are essentially inert under reactions conditions. Suitable solvents include dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMA), and N-methylpyrrolidone (NMP).
• Reaction temperatures for solution grafting are generally in the range of 100°-220° C. and more preferably 140°-180° C. Reaction times are generally in the range of 10 minutes to 24 hours and more preferably 1-10 hours.
• Reaction temperatures for melt grafting are generally in the range of 100°-220° C. and more preferably 180°-210° C. Reaction times are generally in the range of 1 minute to 10 hours and more preferably 1-30 minutes.
• EHMDO 5-ethyl-5-hydroxymethyl-1,3-dioxane
• EHMDO (14.6 g., 0.1 mol.) was placed in a 50 ml three necked flask fitted with a dropper funnel and a drying tube.
• Acryloyl chloride (9.05 g., 0.1 mol.) was added dropwise into the flask over a period of 15 minutes while being cooled in an ice bath.
• the generated hydrogen chloride was removed with either nitrogen gas or a water aspirator.
• the reaction mixture was stirred at room temperature for four hours and at 60°-70° C. for one additional hour under a nitrogen atmosphere.
• the reaction mixture was then extracted with water (4 ⁇ 50 ml).
• the water layer was separated and the product was dried overnight with MgSO 4 . After filtering out the solid MgSO 4 , the product was distilled with a Widmer column under vacuum. The distillate, which NMR spectra confirmed to be monomer MIII, was then collected.
• EHMDO 88 g., 0.6 mol
• acrylic acid 36.4 g., 0.5 mol.
• p-toluene sulfonic acid monohydrate 0.5 g.
• hydroquinone 0.1 g
• toluene 50 ml
• the reaction mixture was stirred at a bath temperature of 160°-180° C. for three hours.
• Toluene-water was collected (water layer, 8 ml). After cooling, the resulting solution was extracted with water (4 ⁇ 150 ml) and the water layer was separated.
• the crude product was dried with MgSO 4 overnight. After filtering the MgSO 4 , the monomer was distilled with a Widmer column under vacuum. NMR spectra confirmed that the product was monomer MIII.
• trioxane used was distilled at 114° C. from sodium metal to remove water with benzophenone as indicator, under the protection of dry nitrogen.
• Two hundred grams of trioxane (Aldrich Co.) were placed in a 500 ml round bottom flask equipped with a magnetic stirrer. The system was heated to about 80° C., then 0.5 gram of sodium metal and 0.3 gram of benzophenone was added under stirring.
• the color of solution changed from light yellow to brown, then to blue. After the appearance of the blue color, the temperature was raised to about 114° C. for distillation. Early portions of the distillate were discarded. The collected later portions had a water content of about 40-70 ppm.
• EHMDO EHMDO
• the test tube contained 22.5 grams of trioxane and was equipped with a magnetic stirrer. The test tube was then placed in an oil bath. When the temperature reached 65° C., 3 ⁇ l of BF 3 . Et 2 O was injected. Within several seconds to several minutes, the solution became immobilized by the growth of polymer throughout the test tube. The copolymerization was allowed to proceed at 60° C. to 65° C. for 20-24 hours.
• Copolymers formed according to this Example III will hereinafter be referred to as Copolymer I.
• Trioxane and a trimethylolpropane formal (TMP) derivative obtained in Example I.C above i.e., an EHMDO ester of acrylic acid, monomer MIII
• TMP trimethylolpropane formal
• Copolymer III Polymers obtained according to this Example V will hereinafter be referred to as Copolymer III.
• Example III-V The crude copolymers obtained in Example III-V above were ground into small particles, then washed with 1% triethanolamine (TEOA) and methanol solution under stirring conditions for 30-40 minutes so as to neutralize the initiator. The copolymer was then filtered, washed with acetone three times, and dried under vacuum at 50° C.
• TEOA triethanolamine
• the unstable end groups of copolymer and the homopolymer of trioxane formed in the copolymerization and the ester groups can be removed by base hydrolysis in the following manner.
• Coplymer I (0.20 g, 0.06 mmole) obtained in Example III above (after base hydrolysis according to Example VI above) was reacted with a monoisocyanate compound (the monoaddition product of 1-hexadecanol and 1,4-benzenediisocyanate, [O ⁇ C ⁇ N--(p-C 6 H 4 )--NH--(CO)--O--(CH 2 ) 15 --CH 3 ], 0.048 g, 0.12 mmole) in dimethylformamide at 160° C. for two hours.
• the product obtained in this manner was characterized by 1 H NMR spectroscopy which indicated that 43% of the hydroxyl functionality of the oxymethylene polymer had reacted with the monoisocyanate compound.
• Copolymer 1 (0.20 g, 0.06 mmole) obtained in Example III above (after base hydrolysis according to Example VI above) was reacted with a monoisocyanate compound (the monoaddition product of diethylene glycol monomethyl ether and 1,4-benzenediisocyanate, [O ⁇ C ⁇ N--(p-C 6 H 4 )--NH--(CO)--O--(CH 2 ) 15 --CH 3 ], 0.028 g, 0.12 mmole) in dimethylformamide at 160° C. for two hours.
• the product obtained in this manner was characterized by 1 H NMR spectroscopy which indicated that >41% of the hydroxyl functionality of the oxymethylene polymer had reacted with the monoisocyanate compound.
• Copolymer I obtained in Example III above was reacted with 1,4-benzene diisocyanate and Elvamide® 8066 (DuPont) in dimethylformamide in two steps. First, Copolymer I, 1,4-benzene diisocyanate, and solvent were reacted for the indicated times. Then Elvamide® 8066 was added to the mixture and reacted for an additional period of time. Reaction charges and conditions are described in Table 3. The products obtained in this manner were characterized by 1 H NMR spectroscopy. The results reported in terms of the percentage of the hydroxyl functionality of the oxymethylene polymers that had reacted with isocyanate functionality are reported in Table 3.
• Copolymer I a hydroxy functional oxymethylene polymer, obtained in Example III above (after base hydrolysis according to Example VI above, 0.50 g, 0.22 mmole) was reacted with 1,4-benzene diisocyanate (0.04 g, 0.25 mmole) and Elvamide® 8066 (1.0 g, 0.25 mole) in two stages.
• Copolymer I and 1,4-benzene diisocyanate were reacted in dimethylformamide (DMF, 5 ml) solvent for two hours at 160° C.
• Elvamide® an amine functional polyamide, was added to the mixture which was reacted for an additional three hours at 160° C.
• Copolymer II obtained in Example IV above (after base hydrolysis according to Example VI above to convert the pendant ester groups to hydroxyl groups) was reacted with DICB in the manner shown in Table 5 below.
• 1 H NMR spectra confirmed that DICB had been grafted onto a side chain of the oxymethylene copolymer backbone.
• Copolymer II a hydroxy functional oxymethylene polymer, obtained in example IV above (after base hydrolysis according to Example VI above to convert pendant ester groups to hydroxyl groups, 0.50 g, 0.06 mmole) was reacted with 1,4-benzene diisocyanate (0.016 g, 0.1 mmole) and Elvamide® 8066 (0.5 g, 0.12 mole) in two stages.
• Copolymer I and 1,4-benzene diisocyanate were reacted in dimethylformamide (DMF, 4 ml) solvent for two hours o at 160° C.
• Elvamide® an amine functional polyamide, was added to the mixture which was reacted for an additional three hours at 160° C.
• Example VII C-1 was repeated except that the charge of DICB was increased to 0.032 g (0.2 mmole). After the grafting reaction, the product was characterized by 1 H NMR spectroscopy which indicated that Elvamide® (1.6 mole %, 2.5 wt %) had been grafted onto the hydroxy functional oxymethylene polymer. The yield of graft polymer based on the amount of copolymer II charged was 92%.
• Copolymer III obtained in Example V above (after base hydrolysis according to Example VI above to convert the pendant ester groups to hydroxyl groups) was reacted with DICB in the manner shown in Table 6 below.
• 1 H NMR spectra confirmed that DICB had been grafted onto a side chain of the oxymethylene copolymer backbone.
• Copolymer III a hydroxy functional oxymethylene polymer, obtained in Example V above (after base hydrolysis according to Example VI above to convert pendant ester groups to hydroxyl groups, 0.50 g, 0.16 mmole) was reacted with 1,4-benzene diisocyanate (0.64 g, 0.4 mmole) and Elvamide® 8066 (1.0 g, 0.25 mole) in two stages.
• Copolymer I and 1,4-benzene diisocyanate were reacted in dimethylformamide (DMF, 5 ml) solvent for two hours at 160° C.
• Elvamide® an amine functional polyamide, was added to the mixture which was reacted for an additional two hours at 160° C.
• Example VII, D-1 was repeated except that the reaction time for the second stage of the grafting reaction was increased from 2 to 17 hours. After the grafting reaction, the product was characterized by 1 H NMR spectroscopy which indicated that Elvamide® (1.9 mole %, 2.7 wt %) had been grafted onto the hydroxy functional oxymethylene polymer. The yield of graft polymer based on the amount of copolymer III charged was 86%.
• Example VII D-1 was repeated except that the charge of DICB was increased from 0.064 g to 0.128 g (0.8 mmole). After the grafting reaction, the product was characterized by 1 H NMR spectroscopy which indicated that Elvamide® (2.9 mole %, 4.0 wt %) had been grafted onto the hydroxy functional oxymethylene polymer. The yield of graft polymer based on the amount of copolymer III charged was 85%.
• the above Examples demonstrate that functional polymers may be grafted with diisocyanate coupling agents onto oxymethylene backbones via the pendant hydroxyl functional groups of the oxymethylene polymers.
• the novel polymers of this invention permit functional polymers to be chemically bound with diisocyanate coupling agents to oxymethylene polymers, particularly oxymethylene copolymers having pendant hydroxyl functionality so as to be useful as modified resins per se, or as compatibilizers in the blending of oxymethylene polymers with other polymers with the same or similar structures as the functional polymers of this invention.

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• Polyurethanes Or Polyureas (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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• 1989
  • 1989-05-12 US US07/350,811 patent/US5043398A/en not_active Expired - Fee Related
• 1990
  • 1990-05-10 EP EP19900305039 patent/EP0397493A3/en not_active Withdrawn
  • 1990-05-11 KR KR1019900006739A patent/KR900018184A/ko not_active Application Discontinuation
  • 1990-05-11 BR BR909002231A patent/BR9002231A/pt unknown
  • 1990-05-11 CA CA002016636A patent/CA2016636A1/en not_active Abandoned
  • 1990-05-12 CN CN90102768A patent/CN1047306A/zh active Pending
  • 1990-05-14 JP JP2123979A patent/JP2846924B2/ja not_active Expired - Fee Related

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